This study examines the effects of replacing fluxing and filler materials with rice straw ash (RSA) in manufacturing porcelain stoneware tile, using the design of experiments (DOE) methodology. The results of the characterization were used to obtain statistically significant, valid regression equations, relating the technological properties of the dried and fired test pieces to the raw materials content in the unfired mixtures. The regression models were analysed in relation to the X-ray diffraction and scanning electron microscopy results and used to determine the most appropriate combinations of traditional raw materials and RSA to produce porcelain stoneware tiles with specific technological properties. The studied range of tile body compositions: clay (40 wt%), feldspar (20–50 wt%), feldspathic sand (5–20 wt%), and RSA (0–25 wt%) was shown to be appropriate for porcelain stoneware tile manufacture